Lubricating composition



Patented Nov. 13, 1951 UNITED STATES PATENT}.

LUe'RIoArmG coMrosrrIoN David E. Adelson, Berkeley;Calififasslgnor to "Shell Development Company, San Francisco,

Califi, a corporation of Delaware No Drawing, Application Qctober 24, 19 4 7,

Serial No. 782,045

- 11 Claims. (01.252465) modern engines and machines operating under ordinary conditions or at high speeds, elevated temperatures, heavylojads and/or other adverse conditions. Some of the deterioration products of truck engines, aviation engines, high speed diesel stuck'isinhibited so that ringsticking; piston engines, and the like. Such additivesserve avery important function because, by modifying this carbonaceous material so that it can 'be readily removed, the tendency of engine parts to become scufiing, scratchingand wearing away of other engine parts, and a material reduction of engine e'ffic'iency, are prevented or materially inhibited. Other additives have been developed for the purpose of acting as detergents-in lubricants. in

lubricants formed during'their use are hard carbonaceou's materials which adhere to'metal surfaces and cause scratching and scuifing of movable metal parts, as well as the sticking of valves and piston rings in engines. In addition, the known lubricants are generally incapable of maintaining a continuous lubricating film between movable metal parts; therefore, their use results in gradual or even rapid wear ;ofmetal parts. The damage thus caused requires replacement of such parts or even the completepyerhauling of engines and machines, thus resulting in expensive loss of productionand time. 4

, the case of the highest quality non-corrosive, 'stable' lubricating oils, which hav'e'b'e'en highly refined, or synthetic'lubri'cants developed forsp'ecific or special uses; it has been observed that such'oils or lubricants are generally highly susceptible to oxidation and deterioration, be-

order to assist 'in' the removal of soot, sludge," varnish, and/or lacquer, formed from deterioration of the oil when subjected to high operating temperatures. Detergents, due to their cleaning action, prevent the accumulation of thesedeleterlous materials and assist in removing those whichare formed; r Anti-wear additives have the property of reducing friction of movable metal parts of the same or different metals. Due to the function exerted or property imparted by such' additives to lubricants, wear caused by direct frictional contact of metals can; be greatly reduced. Also, additives have been developed to withstand extreme pressures, disperse :impurities, solubilize gertain additives and the like. r

The development of the large number of various additives has been due to the fact'that most,.

if not all such additives are capableof function- 7 ing in substantially only one specific manner.

coming progressively more corrosive when'used in engines and machines even under ordinary operating conditions. 5

To improve the lubricating properties of mineral oils and synthetic lubricants it has become the practice to incorporate into these various lubricants at least one and in most cases more than one addition agent, which additives have the effect or property of inhibiting deterioration of lubricants and impart to them certain beneficial Very few lubricant additives have the ability of improving a lubricant in more than-just one respect. Thus, a good anti-oxidant'might not be able to inhibit lacquer and varnish formation on piston rods, or to act as a detergent or corrosion inhibitor. In many cases-itis found that an additive possesses very good properties in one respect, but is detrimental as an additive in another respect. Thereforethe-useof still other additives is frequently required to-obtain a relatively good stable lubricant. The combination of properties. Thus, additives have been specifically developed to have 'the property of inhibiting-corrosion of alloyed bearings such as copper-lead,

cadmium-silver and the like, used in automotive, diesel and aircraft engines. Acidic. oxidation or decomposition components formed in lubricants additives in lubricants whereinfeach additive exerts its influence without interfering with the function of other additives isa difficult matter to attain. ,In, most cases, additives co-react or interfere with each other. To prevent this, great care must be taken in selecting the additives, mixing them in specific proportions and continuously watching and replacing additives which have stopped functioning or have deteriorated.

It is an object of this invention to improve; the lubricating properties of various p lubricating bases by the addition thereto ofa minor amount of a multi-functiona1 materiaL Another object of this invention is to add to compounded or doped lubricants a multi-functional material whereby a synergistic effect is produced, resulting in a product of accentuated and improved properties. Another object of this invention is ing oils, syntheticlubricants and? the like, a. multL functional material so as 'to inhibit oxidation and corrosion and prevent the formation of sludge varnish and lacquer in said lubricants even un-' '5 der adverse operating conditions.

Stillanother' object of this invention is ,to use in lubricating compositions, a multi-functional. material. Whichff i prevents ringsticking as well as the sticking ot other engine parts due to deterioration of the lubricant. Also it is an object of-th is inventiqn to use in oleaginous materials, e. g. in lubricating compositions, a multi-functional materialmhieh inhibits wear, scufling, scratching and other damage to engine. parts. Furthermore, it is. an. object of this invention'to. provide. novel multii-funotional improving and enhancing additives for lubricating bases. Qther obieetsfof thisinvention will appear as the description proceeds.

Totheaccomplisment of the foregoing and-related ends, this. invention. consists'of features which willbe hereinafter iully described, and particularly pointedout. inthe claims, the following' description settingfforth-in detafl'certain. e bodiments of the invention, these-being merely. illustrative of the, principle: of the present in.- vention; 7 V v Broadly stated, this invention. directed-to the use, in lubricants, of reactionproduotsobtained byreacting organic -.compoundswith hydrogen sulfide in the-presence of ammonium .hydrosul fide, and then treating said reactionproductswith. phosphorus and halogen containing. agents; suc as the. phosphorus halides and. phosphorusoxy halides. and the ke. Among the-organic com pounds. which can. he used to: form reaction productsof this invention are a I. ALIPHATIC HYDRoc mao s- Acyclic compounds A. Saturated paraffinic hydrocarbons above 6 car bonatomssuchas a 1 Q v hexane heptane octane nonane tetradecane hexadecane eicosane tetracosane and the like.

B. Unsaturated paraffinic hydrocarbons above 6 carbon atoms such as hexylene heptylenel j, polyolefines:

which may be broadly termed polyalkcnes, and include polypropene, polypentenes as 3 well as branched chain unsaturated hydro.- carbons' such as iso-olefine's and'iso-polyoleflnes.

Cyclic compounds A. Saturated cyclobutane. cyclohexane cyclo-octane and the like.

B. Unsaturated cyclopentadiene cyclohexene cyclo-octene and the like.

A. benzene napthalene j anthracene phena hre bi-phenyl V di-phenylmethane.

stilbene and the; like. 3. alkyl' y mxy amine nitro V nitro'sohalogen carbox-yl. "mercaptan. substituted aromatic compounds. ofgroup-1m. ,and thelilre.

III. CYCLIC TERPENES ymene. .limonene.

inene bornylene.

methene terpinolene terpin .menthol menthone isoborneol' V camphor IV., HETLIERQQYCLIC COMPOUNDS furan' iurfural iur'furyl alcohol -furoi'c acid pyrone pyridine picolinic acid nicotinic acid 'ino'rpholine courarone and the like. Both, the cyclic terpenes,v and the heterocyclic compounds canlhave attached thereto substituent radicals. such as alkyl andalkenyl radicals, hydroxy .andhalogen groups, and the like.

. V. ALCOHOLS A. Aliphatic (saturated and unsaturated) amyl alcohol hexyl. alcohol heptylaleohol octyl. alcohol decyl alcohol dodecyl alcohol octadecyl alcoholcarnaubyl alcohol. oleyl alcohol Poly-hydric. aliphatic alcohols 0. Cyclic alcohols naphthenic alcohol D. Natural occurring alcohols and synthetic al-' cohols Alcohols as found in wool tat, sperm oil Alcohols produced by oxidation of hydro- 6 carbons, e. g.

paraflin wax sweat wax petrolatum and the like.

VI. PHENOLIC COMPOUNDS phenol alkyl phenol catechol resorcinol pyrogallol VII. ACIDS A. Aliphatic (mono and polycarboxylic and hydroxy substituted acids and the like) capric undecylic lauric myristic palmitic stearic arachidic acids;

acrylic sorbic oleic linoleic linolinic acids;

hydroxy stearic di and tri hydroxy stearic ricinoleic acids;

alkyl malonic acid alkyl succinic acid alkyl glutaric acid glycolic acid pyruoic acid phthalonic acid lactic acid alkyl maleic acid alkyl malic acid alkyl tartaric acid alkyl citric acid keto acids suberic acid alkyladipic acid tartronic acid and the like, acids 'produced by oxidation of hydrocarbon e. g. parafiin wax and the like.

B. Aromatic acids benzoic salicylic cinnamic hydrocinnamic phthalic naphthoic abietic aromatic and sulfonic acids derived from petroleum hydrocarbons, mandelic acid, and the like;

phenyl acetic acid phenyl steinic acid naphthyl stearic aci resinic acid 6 Both the aromatic and aliphatic acids of group VIE can have attached thereto substituent groups as suggested under groups II, III, and IV.

VIII. ESTERS Esters contemplated for use in this invention may be obtained by reactioning any of the compounds listed under group V'andVI and their derivatives, with any of the acids listed under group VII.

IX. ETHERS The ethers contemplated for use in this invention may be symmetrical, unsymmetrical, or mixed ethers of dialkyl ethers, alkyl-aryl ethers, aryl ethers and the like. Specifically it is desirable to use:

X. E'I'HERS A. Aliphatic (saturated and unsaturated) ethyl vinyl ether ethyl propenyl ether methyl isopropenyl ether ethyl isopropenyl ether methallyl ether ethyl allyl ether n-propyl allyl ether isopropyl allyl ether 4-ethoxy-1-butene G-ethoxy-l-hexene ethyl propargyl, etc.

' divinyl ether, diallyl ether dicrotonyl ether, dimethylallyl ether di-isopropenyl ether di(alpha-methylallyl) ether (l-butene-B-yl) (2-butene-4-yl) ether dihexaryl ether allyl (2-methyl-4-pentene-2-yl) ether allyl linalyl ether B. Cyclic and poly-ethers ethylene oxide propylene oxide acetal dioxan and the like.

0. Aromatic ethers allyloxyphenyl ether anisole, phenetole, diphenyl, dixenyl, di-

naphthyl ethers benzyl phenyl ether cardanoxyethanol benzyl ether allyl-alpha phenyl vinyl ether allyl phenyl ether and the like.

D. Substituted ethers alkyloxy ethers of polyhydroxy aromatics such as resorcinal, pyrogallol, and the like.

XI. ALDEHYDES A. Aliphatic (saturated and unsaturated) acetaldehyde propionaldehyde butyraldehyde caproaldehyde and the like; acrolein crotonaldehyde citral, etc.

B. Aromatic benzaldehyde cinnamaldehyde salicylaldehyde naphthaldehyde vanillin, etc.

L xn xrwonms; A. Aliphatic -(saturated; and iinsatiiratedy acetone, abutanone; hexanone, oleone, palmitone, methyl ethyl ketone, methyl propyl'ketone, 'bu'tyrone, butenone; pentanone, phorone,"pentanedrone', mesityl oxide," 'diethyl 'ketone, 3-methyl-heptanone; di isobutyl k'etone; diacetone a1- cohoLandthelike.

Aromatic acetophenoneh propiophenone 1 dibenzyl'ketone benzyl phenyl ketone benzophenone and thelike.

C. Cyclic ketones cyclobutanone, cyclohexanone, carvomenthone, menthone, cyclopentanone pulegone; carvone,;musoone, quinones, cycloheptanone, pure isophorone, and isophorone bottoms-the manufacture of which will be fully described hereinafter. I

XIII. NATURAL FATS; 011 s AND THEIR DERIVATIVES AND'QMISCELI tall oiLarid the like.

B. Petroleum hydrocarbons suchfasr naphtha mineral seal oil kerosene 7 as oils, etc.

XIV. Metal saltsand"organic bases'of organic materials listed in any of the above' groups, their mixtures, or variouscombinations may be treated with hydrogen sulfide in presence of ammonium hydrosulfide' "and" thereafter reacted with a phosphorus-halogen containing "agent. Metal bases include those of the alkali'metalsjCu, Mg, Ca, Ba, Zn, Cd, AL Sn, Pb,*C'r, lVI n;,1Fe, Ni, G0, etc. Organic bases-include various nitrogen bases as primary, secondary, tertiary, and'- 'quaternary amines. f

Among the specific and preferred compounds contemplated for reacting with hydrogen'sulfide in the presence of ammonium hydrosulfide and. further treating said product-witha-phosphorus and halogen containing agent, may; be mentioned: stilbene, oleic acid, ammonium oleate, potassium oleate, ammoniumundepyle'nate, ethyl rapeseed oil, peanut oil, dehydrated master oil,

and tall oil as Wfill, as, ,Wax'olefins cinnamyl alco- 6 molecular weightsaturated and; unsaturated ketones, diacetone alcohol, 'nre'sityl"oiz'ide, ethyl oleate, ethyl cinnamate;a-::cinnamaldehyde, and isophorone bottoms, the production and identification of which clatter, :will 'be-rIully. described bel wt. I Isophor nebottomsare primarily high molecular Weight unsaturated ketones having at least 12 and preferably more-than} 1'8' rbon atoms in the molecule. These raauc y be obtained by condensation of acetone" in acaustic solution under elevated temperatu'if andip'ressure. Specifically the product is ob nableby condensing aceto e in"a 3() '%-'fto' 60%C1iiS-tib's0lilti0h at? a; temperatur rdi'igiil'g betWefi-hbut C. and

, abo'utI'Z'O QCIJand-under-a pres'sure-of frofriabout Y 300 "rzr abour soo pounds' pers uare inch. The V resultantproduct is subjected t distillatio'n to re move distillable ketones afid other constituents" and impurities. The product remaining in the still is preferably purified'by filtration, solvent ea ment; a dcompr ses; r e unsatura d cycl e 9n si qizli im pularew isht;pr f ably referred to as crude isophoro The term isophorone bottomsf, herein is usuallya complex mixture ular Weight unsaturated cyclic keton at least 12 and preferably more, th 7 atoms in the molecule. The product is not to be confused with straight fo'p which is specifically 3,5,5ti'iiflthylf 2-one-1, which is an unsaturated "by containing only nine carbon atoms the molecule. Isophorone bottoms produced b' "ondensaw tion of acetone under conditions refie d to above 7 includes within its scope anya'rid a1 cyclic ketones containing atleast 12 and preferably more than 18'carbonatomsandhaving generally the chemical structural configuration of isophorone as well as the chemical' structural configuration resulting'from urther condensation.

Crude isophorone bottoms can be -fra tionated by distillation. The bottoms can thenbe filtered and purified and comprise essential-lyi fisaturated cyclic ketones containing at least "as more. carbon atoms in the molecule an'd referred to as crude, hydrolyzed isoph one bottoms. Thismaterial can be subjected;to d1st1 1 lyzed.; isophorone traction has a boiling point of about lo? C at 1Q mm nr erculypressure and consists of a mixture of unsaturated cyclic ketones containing between 15 tolB-parb nsatems in the molecule. The residue r-is;reierrecrto;as topped, crude hydrolyzed isophoronev bottoms; and similar to topped crude isophorone-:wbottoms.

saturated V s I 1 latiomto split it into two fractions. The distilledhydro- This residue comprises essentially unsaturated cyclic ketones of at least carbon atoms and higher in the molecule. Crude isophorone bottoms can be also subjected to condensation over solid sodium hydroxide to yield two types of resinous materials. -The first resinous fraction or soft resin has a viscosity at 210 F. of about 25-26 centistokes and an average molecular weight of from 320 to 350. The heavier fraction or medium resin has a viscosity at 210'F. of about 25-26 centistokes and an average molecular weight of from 320 to 350. The heavier fraction or medium resin has a viscosity at 210 F. of

about 80 to 120 centistokes and an average molecular weight of from 370 to 390. The unsaturated cyclic ketones can be hydrogenated to produce saturated cyclic ketones. All of the various saturated and unsaturated cyclic ketone fractions obtained in the manner described above can be used. All of the various saturated and unsaturated cyclic ketone fractions obtained in the manner described above can, in accordance with one phase of this invention, be first reacted with hydrogen sulfide in the presence of ammonium'hydrosulfide and the reaction product thus formed may then be further treated with a phosphorus halide to form desired final reaction products having outstanding properties as improving agents for lubricants. Among the phosphorus halides which can be used to treat the initial reaction, namely the reaction of hydrogen sulfide-ammonium hydrosulfide and an organic compound are: PO13, PCls, PFBrz, PBra, POBra, POCh, POFb, POFClz, POFBrz, POFzCl, BOFzBr, P203014, POzCl, PClzBr, P8013, P13, P2I4 and the like.

In carrying out the final reaction product it is preferable to'do it in the presence of a peroxide catalyst which may include: hydrogen peroxide, benzoyl peroxide, lauroyl peroxide, tetralin peroxide, urea peroxide, butyrl peroxide, diethyl peroxide, di-tert-buty1 peroxide, diacyl peroxide, acetyl benzoyl peroxide, propionyl peroxide, oyclohexanone peroxide, ascaridole, alkali and alkaline earth metal peroxides or mixtures thereof can be used.

The products formed by the reaction of hydrogen sulfide-ammonium hydrosulfide with an organic compound can be prepared at room or elevated temperatures, preferably in closed vessels. The use of elevated temperatures apparently only speeds up the reaction. However, the cost of fuel and special equipment outweighs this feature, and it has been ordinarily found more advantangeous to simply allow the ammonium hydrosulfide-hydrogen sulfide organic compound reactions to take place at room temperature in closed vessels for the necessary period of time,

. e. g. from one week to one month or more, de-

pending upon the organic material being treated.. The final reaction product which is formed by treating the reaction products of ammonium hydrosulfide-hydrogen sulfide and an organic Analysis of i V 1gyclic tone Analysis of V pp Product crude isophorone ottom) Per cent by Sulfur 7.2 (5) Percent by wt. Carbon 76.2 (1) 79 5 (9) Percent by wt.- Hydrogen 9.6 (2) 9 8 (9) Per cent by wt. Nitrogen 0.26 Per cent by wt. oxygen .(by difference).-. '6. 6 (6) 10 6 (2) M01. wt-.-"(ebu111scop1c determination in 352 16 10 .EXAMPLE I A. Initial"reacttonproduct of hydrogen sulfide in. the presence of ammonium hydrosulfide with topped, crude isophorone bottoms Isopropyl alcoholf(700' cc.) contained in a 4- liter, thick-walled" suction flask, was saturated with ammonia followed by dry hydrogen sulfide. A solution of 238.5'gram's of topped, crude isophorone bottoms in 350 cc. isopropyl alcohol was"a'dde'd and the resulting solution was saturated with hydrogen sulfide. The side-neck and mouth of the fiask were then closed and the flask wasfa llowed to stand for a 'week with infrequentl'shaking. Upon opening the flask a partial vacuum wasdiscovered. The reaction mixture was filtered to remove impurities and the isopropyl' alcohol was removed from the filtrate byevapora'tion: The residue was dissolved in 500-cc=of a'non aromatic hydrocarbon having a boiling range'of between about 164 F. and 233 1 .v and washed with water. After removal of the solvent in a current of nitrogen gas on a steanibath, a verylviscous sticky mass was obtained', said mass possessing a pleasant odor and exhibiting much .less flow at room temperature than..did;:thestartin'g materials. The product was :oil'-soluble and on analysis, contained:

tert-butyl peroxide were admixed in a suitable vessel and the mixture'was heated and stirred compound with any of the previously mentioned phosphorus halides can be carried out at elevated temperatures of between about C. and about 200. C. and preferably between about C.

and about C- and if desired in the presence "ofa suitable inert solvent and a peroxide cat- 3 h Spirit Of the invention 7 j H on asteam bath for about 24 hours. At the end of the reaction period, the desired product was extracted with a non-aromatic hydrocarbon having a boiling range of between about 164 F. and 233 F." The solutionwas filtered and the filtrate evaporated at steam temperature in a current of carbondioxide- The resultant product was a viscous mass containing a substantial amount of sulfur, phosphorus, and chlorine.

A. Initial reaction product of ammonium hydrof sulfide-hydrogen sulfide and topped, crude isophorone bottoms j ,This reaction produotwas prepared in an isopropyl alcohol. medium (1315 cc.) using about 295"gm. oftopped, crude isophorone bottoms in an autoclave for5 /a hours at 96 C. to 101.5 C. Theproduct was then treated as indicated in Example I, part'A, and the'analysis of the .product was as' fo1lows:"

I i An excellent metallic detergent for the present purpose is the calcium salt of oil-soluble petroleum sulfonic acids. This may be present advantageously in the amountof about 0.025% to 0.2% sulfate ash; Also alkaline metal salts of alkyl phenol-aldehyde condensation reaction products are excellent. detergents;

Anti-oxidants comprise several types, for-example, alkylphenols such as 2,4,6-trimethyl phenol, pentamethyl phenol, 1 2,4-dimethyl-6- tertiary-'butyl phenol, 2,4-dimethyl-6-octyl phenol, 2,6-di-tertiary-butyli-methyl-phenol, 2,4,6-

amino Corrosion inhibitors or anti-rusting compounds may also be present, such as dicarboxylic acids of 16 and more carbon atoms; alkali metal and alkaline earth salts of sulfonic acids and fatty acids; organic compounds containing an acidic it'riaryl, alkyl-hydroxy aryl, or aralkyl phosphates,

'thio-phosphates orphosphites and the like; neutral aromatic sulfur compounds of relatively high boiling temperatures such as diaryl sulfides, diaryl disulfiides, alkyl aryl disulfides, e. g. diphenyl sulfide, diphenol sulfide, dicresol sulfide, dixylenol sulfide, methyl butyl diphenol sulfide, dibenzyl sulfide, corresponding diand trisulfides, and the like; sulfurized fatty oils or esters of fatty acids and monohydric alcohols, e. g. sperm oil, jojoba oil, etc; in which the sulfur is strongly bonded; sulfurized long chain olefins such as may be obtained by dehydrogenation or cracking of wax; sulfurized phosphorized fatty oils or acids, phosphorus acid esters having sulfurized organic radicals, such as esters of phosphoric or phosphorus acids with sulfurized hydroxy fatty acids; chlorinated hydrocarbons, such as chlorinated parafiin, aromatic hydrocarbons, terpenes, mineral lubricating oil, etc.; or chlorinated esters of fatty acids containing the chlorine in position other than alpha position.

Additional ingredients may comprise oilsoluble urea or thiourea derivatives, e. g. urethanes, allophanates, carbazides, carbazones, etc.; polyisobutylene polymers, unsaturated polymerized esters of fatty acids and monohydric alcohols and other high molecular weight oilsoluble compounds.

Depending upon the additive used and conditions under which it is used, the amount of additive used may vary from 0.01 to 2 or higher. However, substantial improvement is obtained by using amounts ranging from 0.1 to 0.5% in combination with phosphorous sulfide-unsaturated cyclic ketone reaction product of this invention.

It is to be understood that while the features of the invention have been described and illustrated in connection with certain specific examples, the invention, however, is not to be limited thereto or otherwise restricted, except by the prior art and the scope of the appended claims.

This application is a continuation-in-part of the co-pending application, Serial No. 718,617, filed December 26, 1946, which has matured into U. S. Patent 2,512,784.

I claim as my invention:

1. A lubricant comprising a major amount of a lubricating oil and a minor amount, sufficient to stabilize said oil against oxidation and corrosion deterioration, of a reaction product obtained by reacting an unsaturated cyclic ketone fraction having at least 12 carbon atoms with hydrogen sulfide and ammonium hydrosulfide, at between about room temperature and about 100 C. and treating the resulting reaction product with a phosphorus halide at between about steam temperature and 200 C. in the mol ratio of around 1 to 4 respectively.

' 2. A lubricant comprising a major amount of mineral lubricating oil and a minor amount, of from'0.1% to 5% by weight, of a reaction product obtained by reacting an unsaturated cyclic ketone fraction having at least 12 carbon atoms with -.hydrogen sulfide and ammonium hydrosulfide at between about room temperature and 100 C. and treating the resulting f reaction, product with phosphorus pentachloride at a temperature of at least 150 C. in the mol'ratio of around 1 to 4 a respectively.

3. A lubricant comprising a major amount of mineral lubricating oil and a minor amount, of from 0.1% to 5% by weight, of a reactionproduct obtained by reacting isophorone bottoms fraction having at least 12 carbon atoms with hydrogen sulfide and ammonium hydrosulfide at between about room temperature and C. and treating the resulting reaction product with phosphorus pentachloride at a temperature of at least C. in the mol ratio of around 1 to 4 respectively.

4. A lubricant comprising a major amount of mineral lubricating oil and a minor amount, of from 0.1% to 5% by weight, of a reaction product obtained by reacting an unsaturated cyclic ketone fraction having at least 12 carbon atoms with hydrogen sulfide and ammonium hydrosulfide at between about room temperature and 100 C. and treating the resulting reaction product with phosphorus oxychloride at a temperature of at least 150 C. in the mol ratio of around 1 to 4 respectively.

5. A lubricant comprising a major amount of mineral lubricating oil and a minor amount, of from 0.1% to 5% by weight, of a reaction product obtainted by reacting isophorone bottoms fraction having at least 12 carbon atoms with hydrogen sulfide and ammonium hydrosulfide at between about room temperature and 100 C. and treating the resulting reaction product with phosphorus oxychloride at a temperature of at least 150 C. in the mol ratio of around 1 to 4 respectively. 4

6. A compounded lubricant comprising a major amount of a mineral lubricating oil and containing an active amount of calcium salt of alkyl phenol-formaldehyde condensation reaction product, calcium salt of petroleum sulfonic acid as detergents, and a small amount of from 0.1% to 5% by weight of a reaction product obtained by reacting an unsaturated cyclic ketone fraction having at least 12 carbon atoms with hydrogen sulfide and ammonium hydrosulfide, at between about room temperature and about 100 C. and treating the resulting reaction product with a phosphorus halide at a temperature of at least 150 C. in the mol ratio of around 1 to 4 respectively.

7. An organic composition having incorporated therein as the essential stabilizing agent the reaction product obtained by first reacting an unsaturated cyclic ketone fraction having at least 12 carbon atoms with hydrogen sulfide and ammonium hydrosulfide at between about room 

1. A LUBRICATING COMPRISING A MAJOR AMOUNT OF A LUBRICATING OIL AND A MINOR AMOUNT, SUFFICIENT TO STABILIZE SAID OIL AGAINST OXIDATION AND CORROSION DETERIORATION, OF A REACTION PRODUCT OBTAINED BY REACTING AN UNSATURATED CYCLIC KETONE FRACTION HAVING AT LEAST 12 CARBON ATOMS WITH HYDROGEN SULFIDE AND AMMONIUM HYDROSULFIDE, AT BETWEEN ABOUT ROOM TEMPERATURE REACTION PRODUCT WITH A TREATING THE RESULTING REACTION PRODUCT WITH A PHOSPHORUS HALIDE AT BETWEEN ABOUT STEAM TEMPERATURE AND 200* C. IN THE MOL RATIO OF AROUND 1 TO 4 RESPECTIVELY. 